CN109876778B - Preparation method of organic porous material - Google Patents
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- 239000011148 porous material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 239000004202 carbamide Substances 0.000 claims abstract description 23
- 239000002608 ionic liquid Substances 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000008014 freezing Effects 0.000 claims abstract description 9
- 238000007710 freezing Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical compound [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 7
- MHXLAKJJNRIVDR-UHFFFAOYSA-N 2,4,6-trihydroxybenzene-1,3,5-tricarboxylic acid Chemical compound OC1=C(C(=C(C(=C1C(=O)O)O)C(=O)O)O)C(=O)O MHXLAKJJNRIVDR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000944 Soxhlet extraction Methods 0.000 claims abstract description 5
- UCYRAEIHXSVXPV-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)indiganyl trifluoromethanesulfonate Chemical compound [In+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F UCYRAEIHXSVXPV-UHFFFAOYSA-K 0.000 claims abstract description 4
- TWNOVENTEPVGEJ-UHFFFAOYSA-K europium(3+);trifluoromethanesulfonate Chemical compound [Eu+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F TWNOVENTEPVGEJ-UHFFFAOYSA-K 0.000 claims abstract description 4
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 claims abstract description 4
- JPJIEXKLJOWQQK-UHFFFAOYSA-K trifluoromethanesulfonate;yttrium(3+) Chemical compound [Y+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F JPJIEXKLJOWQQK-UHFFFAOYSA-K 0.000 claims abstract description 4
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims abstract description 4
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 6
- -1 2-hydroxyethyl trimethyl ammonium tetrafluoroborate Chemical compound 0.000 claims description 5
- FHCUSSBEGLCCHQ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CCO FHCUSSBEGLCCHQ-UHFFFAOYSA-M 0.000 claims description 4
- LDWOOZOWGNCQRI-UHFFFAOYSA-N 2-hydroxyethyl(trimethyl)azanium;nitrate Chemical compound [O-][N+]([O-])=O.C[N+](C)(C)CCO LDWOOZOWGNCQRI-UHFFFAOYSA-N 0.000 claims description 3
- 125000003172 aldehyde group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000003708 ampul Substances 0.000 description 27
- 238000001179 sorption measurement Methods 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- BUVBYQUZAIPDHT-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S.NC(N)=S BUVBYQUZAIPDHT-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007210 heterogeneous catalysis Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A preparation method of an organic porous material comprises the following steps: adding an ionic liquid and 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid into a reaction container, adding a catalyst, ultrasonically mixing uniformly, placing the reaction container in liquid nitrogen, freezing for 1-3 min, vacuumizing to 0.01-1 pa, sealing the reaction container, and reacting for 24-72 h at 90-150 ℃ to obtain a product; the ion-like liquid is prepared from a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is one of urea and thiourea; the catalyst is one of scandium trifluoromethanesulfonate, europium trifluoromethanesulfonate, indium trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, yttrium trifluoromethanesulfonate and zinc trifluoromethanesulfonate; washing the product with a solvent, performing Soxhlet extraction for 12-48 h, and filtering; drying under vacuum condition to obtain the organic porous material. The method can avoid the use of volatile and toxic organic solvent, and improve environmental protection performance.
Description
Technical Field
The invention belongs to the technical field of chemical catalysis, and particularly relates to a preparation method of an organic porous material.
Background
The economic development and industrialization of the human society are largely dependent on the combustion and utilization of non-renewable energy sources such as petroleum, coal, and natural gas. Large amount of CO produced by combustion2The greenhouse effect and global climate change are seriously influenced, such as the occurrence frequency of extreme weather events is increased, polar glaciers are greatly reduced, the number of species is reduced, and the like. CO 22The adsorption and storage of (A) is currently reducing atmospheric CO2One of the solutions with more effective contents is the focus of research in recent years.
CO adsorption commonly used at present2The method comprises solution absorption, solid material adsorption, membrane technology and the like. The absorption of the solution is limited by the temperature, and the membrane is generally high in cost, so that the adsorption of the solid material shows great advantages. The organic porous material is synthesized by designing various construction units and connection modes, mainly consists of light elements (C, H, B, O, N and the like), has the advantages of low skeleton density, large specific surface area, high stability, adjustable pore diameter, easiness in functionalization and the like, is widely concerned in the fields of gas adsorption and separation, heterogeneous catalysis, photoelectric devices, biosensors and the like, and is particularly suitable for CO (carbon monoxide) adsorption and separation, heterogeneous catalysis, photoelectric devices, biosensors and the like2Has great application in the field of adsorption and separationAnd (4) foreground. At present, the organic porous material is obtained by reacting micromolecular monomers in a volatile and toxic organic solvent, and the environmental protection property is poor.
The eutectic solvent, also called ionic liquid, is a novel green solvent, is formed by mutual crosslinking of two chemical components through hydrogen bond interaction, has a melting point lower than that of any one of the components, and can be used as a reaction solvent and even used as a precursor for synthesizing a carbon-containing material.
Disclosure of Invention
The invention aims to provide a preparation method of an organic porous material, which can avoid using an organic solvent with volatility and toxicity and improve the environmental protection performance; the organic porous material prepared by the method can improve the adsorption performance to carbon dioxide.
In order to achieve the above object, the present invention provides a method for preparing an organic porous material, comprising the steps of:
(1) adding a certain amount of ionic liquid and 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid into a reaction container, adding a certain amount of catalyst, ultrasonically mixing uniformly, then placing the reaction container into liquid nitrogen, freezing for 1-3 min, vacuumizing to 0.01-1 Pa, sealing the reaction container, and reacting for 24-72 h at 90-150 ℃ to obtain a product; the ionic liquid is prepared from a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is one of urea and thiourea; when the hydrogen bond donor is urea, the hydrogen bond acceptor is one of 2-hydroxyethyl trimethyl ammonium chloride, 2-hydroxyethyl trimethyl ammonium fluoride, 2-hydroxyethyl trimethyl ammonium nitrate and 2-hydroxyethyl trimethyl ammonium tetrafluoroborate; when the hydrogen bond donor is thiourea, the hydrogen bond acceptor is 2-hydroxyethyl trimethyl ammonium chloride; the catalyst is one of scandium trifluoromethanesulfonate, europium trifluoromethanesulfonate, indium trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, yttrium trifluoromethanesulfonate and zinc trifluoromethanesulfonate;
(2) washing the product with a solvent, performing Soxhlet extraction for 12-48 h, and filtering;
(3) heating to 100-150 ℃ under vacuum condition, and drying for 10-24 h to obtain the organic porous material.
Preferably, the molar ratio of the catalyst to aldehyde groups in the 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde is 0.06-1.5; the mass ratio of the ionic liquid to the 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid is 10-200.
Further, the preparation method of the ionic liquid comprises the following steps: and (2) mixing the hydrogen bond donor and the hydrogen bond acceptor according to the molar ratio of 2: 1, adding the mixture into a reaction container, heating to 80-100 ℃, and reacting for 0.5-2 h to obtain uniform and stable ionic liquid.
Preferably, the solvent used in step (2) is two or three of water, tetrahydrofuran and methanol.
Preferably, the reaction in the step (1) is carried out at 120 ℃ for 72h to obtain the product.
Compared with the prior art, the invention has the following advantages:
(1) the invention adopts the ion-like liquid as the reaction solvent, the ion-like liquid is a novel green solvent, the preparation is generally carried out at normal temperature and normal pressure, the operation is simple, the auxiliary technology and the purification are not needed, and simultaneously, the raw materials (hydrogen bond donor and hydrogen bond acceptor) for preparing the ion-like liquid are easy to obtain and the cost is low. The ionic liquid has the advantages of low price, easy obtaining, good thermal stability and chemical stability, extremely low vapor pressure, no toxicity, no harm, biodegradability and the like;
(2) the hydrogen bond donor (urea or thiourea) is not only used as a raw material for preparing the ionic liquid, but also used as a reaction monomer to react with 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde to synthesize the organic porous material, so that the types of reactants are reduced, more processes of removing impurities or unreacted raw materials are reduced, and in addition, the urea and thiourea are low in purchase price, so that the production cost is further reduced;
(3) the preparation method is simple, low in cost and good in environmental protection, and the prepared organic porous material has excellent adsorption performance on carbon dioxide.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example one
Adding 0.083mol of Urea (Urea) and 0.042mol of 2-hydroxyethyl trimethyl ammonium chloride (ChCl) into a round-bottom flask, and heating and reacting at 80 ℃ for 30min to obtain uniform and stable ChCl-Urea ionic liquid with a melting point: 12 ℃ and the reaction formula is as follows:
example two
Adding 0.083mol of Thiourea (Thiourea) and 0.042mol of 2-hydroxyethyl trimethyl ammonium chloride (ChCl) into a round-bottom flask, heating and reacting at 80 ℃ for 120min to obtain uniform and stable ChCl-Thiourea ionic liquid, wherein the melting point is as follows: 69 ℃, the reaction formula is as follows:
EXAMPLE III
Adding 0.083mol of Urea (Urea) and 0.042mol of 2-hydroxyethyl trimethyl ammonium fluoride (ChF) into a round-bottom flask, and heating and reacting at 100 ℃ for 30min to obtain uniform and stable ChF-Urea ionic liquid, wherein the melting point is as follows: 1 ℃ and the reaction formula is as follows:
example four
0.083mol of Urea (Urea) and 0.042mol of 2-hydroxyethyl trimethyl ammonium nitrate (ChNO)3) Adding into round-bottom flask, heating at 90 deg.C for 50min to obtain uniform and stable ChNO3-Urea-type ionic liquids, melting point: at 4 ℃, the reaction formula is as follows:
EXAMPLE five
0.083mol of Urea (Urea) and 0.042mol of 2-hydroxyethyl trimethylammoniumtetrafluoroborate (ChBF) are mixed4) Adding into round-bottom flask, heating at 80 deg.C for 60min to obtain uniform and stable ChBF4-Urea-type ionic liquids, melting point: at 67 ℃, the reaction formula is as follows:
EXAMPLE six
Adding 1.5g of the ion-like liquid ChCl-Urea prepared in the embodiment I and 0.1mmol of 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid (TFP) (0.021g) into an ampoule bottle, adding 0.3mmol of scandium trifluoromethanesulfonate, carrying out ultrasonic mixing uniformly, placing the ampoule bottle in liquid nitrogen, freezing for 1-3 min, vacuumizing for 0.01-1 Pa, repeating the operation for 3 times to ensure the vacuum state in the ampoule bottle, sealing the bottle opening by flame, and finally placing the ampoule bottle in a container at 120 ℃ for reaction for 72h to obtain the product. After the reaction is finished, washing the product with water, tetrahydrofuran and methanol for 3 times respectively, then extracting the product with tetrahydrofuran in a soxhlet manner for 12 hours, and finally drying the product in vacuum at 100 ℃ for 12 hours to obtain brownish red powder, namely the TFP-Urea porous material, wherein the yield is 97%, and the BET specific surface area is 725m2(ii) in terms of/g. The infrared spectrogram analysis shows that: at 1204cm-1And 1531cm-1Characteristic peaks of C-N and C ═ C, respectively, appear, indicating the formation of porous materials based on the aldehyde-amine condensation and enol-to-ketone interconversion. The reaction formula is as follows:
EXAMPLE seven
0.21g of the ionic liquid ChCl-Thiourea prepared in the example II and 0.1mmol of TFP (0.021g) are added into an ampoule bottle, 0.018mmol of europium trifluoromethanesulfonate is added and mixed uniformly by ultrasonic, the ampoule bottle is placed in liquid nitrogen for freezing and vacuuming, the operation is repeated for 3 times to ensure the vacuum state in the ampoule bottle, the opening of the ampoule bottle is sealed by flame, and the ampoule bottle is placed in a container at 90 ℃ for reaction for 72 hours. After the reaction is finished, washing the product with water and tetrahydrofuran for 3 times respectively, then performing soxhlet extraction with tetrahydrofuran for 24 hours, and finally performing vacuum drying treatment at 100 ℃ for 24 hours to obtain brownish red powder, namely the product, wherein the yield is 90%, and the BET specific surface area is 480m2(ii) in terms of/g. The infrared spectrogram analysis shows that: at 1203cm-1And 1534cm-1Characteristic peaks of C-N and C ═ C, respectively, appear, indicating the formation of porous materials based on the aldehyde-amine condensation and enol-to-ketone interconversion. The reaction formula is as follows:
example eight
2.1g of the ionic liquid ChF-Urea prepared in the third embodiment and 0.1mmol of TFP (0.021g) are added into an ampoule bottle, 0.3mmol of indium trifluoromethanesulfonate is added and uniformly mixed by ultrasonic, the ampoule bottle is placed in liquid nitrogen for freezing and vacuuming, the operation is repeated for 3 times to ensure the vacuum state in the ampoule bottle, the opening of the ampoule bottle is sealed by flame, and the ampoule bottle is placed in a container at 150 ℃ for reaction for 24 hours. After the reaction is finished, washing the product with water and methanol for 3 times respectively, then performing soxhlet extraction with tetrahydrofuran for 48h, and finally performing vacuum drying treatment at 150 ℃ for 10h to obtain brownish red powder, namely the product, wherein the yield is 92%, and the BET specific surface area is 515m2(ii) in terms of/g. The infrared spectrogram analysis shows that: at 1206cm-1And 1533cm-1Characteristic peaks of C-N and C ═ C, respectively, appear, indicating the formation of porous materials based on the aldehyde-amine condensation and enol-to-ketone interconversion. The reaction formula is the same as that of example six.
Example nine
1.0g of the ionic liquid ChNO prepared in example IV3Adding Urea and 0.1mmol TFP (0.021g) into an ampoule bottle, adding 0.09mmol ytterbium trifluoromethanesulfonate, ultrasonically mixing uniformly, placing the ampoule bottle in liquid nitrogen for freezing, vacuumizing, repeating the operation for 3 times to ensure the vacuum state in the ampoule bottle, sealing the opening of the ampoule bottle by flame, and placing the ampoule bottle in a container at 120 ℃ for reacting for 72 hours. After the reaction is finished, washing the product with water, tetrahydrofuran and methanol for 3 times respectively, then extracting the product with tetrahydrofuran in a soxhlet manner for 12 hours, and finally drying the product in vacuum at 100 ℃ for 12 hours to obtain brownish red powder, namely the product, wherein the yield is 94%, and the BET specific surface area is 550m2(ii) in terms of/g. The infrared spectrogram analysis shows that: at 1201cm-1And 1530cm-1Characteristic peaks of C-N and C ═ C, respectively, appear, indicating the formation of porous materials based on the aldehyde-amine condensation and enol-to-ketone interconversion. The reaction formula is the same as that of example six.
Example ten
4.2g of the ion-like liquid ChBF prepared in example V was taken4Adding Urea and 0.1mmol TFP (0.021g) into an ampoule bottle, adding 0.24mmol yttrium trifluoromethanesulfonate, uniformly mixing by ultrasonic, placing the ampoule bottle in liquid nitrogen for freezing, vacuumizing, repeating the operation for 3 times to ensure the vacuum state in the ampoule bottle, sealing the opening of the bottle by flame, and placing the ampoule bottle in a container at 120 ℃ for reacting for 72 hours. After the reaction is finished, washing the product with water, tetrahydrofuran and methanol for 3 times respectively, then extracting the product with tetrahydrofuran in a soxhlet manner for 12 hours, and finally drying the product in vacuum at 100 ℃ for 12 hours to obtain brownish red powder, namely the product, wherein the yield is 94%, and the BET specific surface area is 600m2(ii) in terms of/g. The infrared spectrogram analysis shows that: at 1206cm-1And 1534cm-1Characteristic peaks of C-N and C ═ C, respectively, appear, indicating the formation of porous materials based on the aldehyde-amine condensation and enol-to-ketone interconversion. The reaction formula is the same as that of example six.
EXAMPLE eleven
Adding 1.0g of the ionic liquid ChCl-Urea prepared in the embodiment I and 0.1mmol of TFP (0.021g) into an ampoule bottle, adding 0.45mmol of zinc trifluoromethanesulfonate, carrying out ultrasonic mixing uniformly, placing the ampoule bottle into liquid nitrogen for freezing, vacuumizing, repeating the operation for 3 times to ensure the vacuum state in the ampoule bottle, sealing the bottle opening by flame, and placing the ampoule bottle into a container at 120 ℃ for reaction for 72 hours. After the reaction is finished, washing the product with water, tetrahydrofuran and methanol for 3 times respectively, then extracting the product with tetrahydrofuran in a soxhlet manner for 12 hours, and finally drying the product in vacuum at 100 ℃ for 12 hours to obtain brownish red powder, namely the product, wherein the yield is 92%, and the BET specific surface area is 650m2(ii) in terms of/g. The infrared spectrogram analysis shows that: at 1203cm-1And 1532cm-1Characteristic peaks of C-N and C ═ C, respectively, appear, indicating the formation of porous materials based on the aldehyde-amine condensation and enol-to-ketone interconversion. The reaction formula is the same as that of example six.
The porous material samples prepared in examples six to eleventh were respectively put into a 9mm quartz tube, vacuum degassing was performed on the samples for 12 hours under the condition of 393K, the samples were transferred to an analysis station after being cooled to room temperature, the temperature was controlled to 273K using a constant temperature water bath, and CO was measured2Adsorption-desorption isotherms. The results are shown in table 1 below:
TABLE 1 porous Material sample CO2Amount of adsorption
As can be seen from Table 1, the porous materials prepared in the above examples have CO content at 273K and 1bar2The adsorption capacity reaches more than 100mg/g and the highest adsorption capacity reaches 194mg/g, which shows that the organic porous material prepared by the invention can adsorb CO2The adsorption performance of (2) is excellent.
Claims (5)
1. The preparation method of the organic porous material is characterized by comprising the following steps of:
(1) adding a certain amount of ionic liquid and 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid into a reaction container, adding a certain amount of catalyst, ultrasonically mixing uniformly, then placing the reaction container into liquid nitrogen, freezing for 1-3 min, vacuumizing to 0.01-1 Pa, sealing the reaction container, and reacting for 24-72 h at 90-150 ℃ to obtain a product; the ionic liquid is prepared from a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is one of urea and thiourea; when the hydrogen bond donor is urea, the hydrogen bond acceptor is one of 2-hydroxyethyl trimethyl ammonium chloride, 2-hydroxyethyl trimethyl ammonium fluoride, 2-hydroxyethyl trimethyl ammonium nitrate and 2-hydroxyethyl trimethyl ammonium tetrafluoroborate; when the hydrogen bond donor is thiourea, the hydrogen bond acceptor is 2-hydroxyethyl trimethyl ammonium chloride; the catalyst is one of scandium trifluoromethanesulfonate, europium trifluoromethanesulfonate, indium trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, yttrium trifluoromethanesulfonate and zinc trifluoromethanesulfonate;
(2) washing the product with a solvent, performing Soxhlet extraction for 12-48 h, and filtering;
(3) heating to 100-150 ℃ under vacuum condition, and drying for 10-24 h to obtain the organic porous material.
2. The method for preparing the organic porous material as claimed in claim 1, wherein the molar ratio of the aldehyde group in the catalyst to the aldehyde group in the 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic aldehyde is 0.06-1.5; the mass ratio of the ionic liquid to the 2,4, 6-trihydroxy-1, 3, 5-benzenetricarboxylic acid is 10-200.
3. The method for preparing the organic porous material as claimed in claim 1 or 2, wherein the method for preparing the ionic liquid is as follows: and (2) mixing the hydrogen bond donor and the hydrogen bond acceptor according to the molar ratio of 2: 1, adding the mixture into a reaction container, heating to 80-100 ℃, and reacting for 0.5-2 h to obtain uniform and stable ionic liquid.
4. The method for preparing an organic porous material according to claim 1 or 2, wherein the solvent used in step (2) is two or three of water, tetrahydrofuran, and methanol.
5. The method for preparing an organic porous material according to claim 1 or 2, wherein the reaction in step (1) is carried out at 120 ℃ for 72 hours to obtain a product.
Priority Applications (1)
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